KR790001342B1 - Process for preparing triazolyl-0,n-acetals - Google Patents

Abstract

Fungicidal title compds. I; R1,R2,R3=same or not H, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl; Ax = 1,2,4-triazolyl-(1), 1,2,4-triazolyl-(4), 1,2,3-triazolyl-(1) were prepd. by redn. of II with NaBH4 in the presence of polar solvent such as THF. Thus, 31.4g W-(4'-chlorphenyl)-W- 1,2,4-triazolyl-(1) -acetophenone, mixed with 3g NaBH4 in MeOH at room temp. for 1hr gave 25g (yield 98%) I R1 = 4'-ClPhO ; R2 = H, R3 = Ph; Az = 1,2,4-triazolyl-(1).

Description

Preparation of triazolyl-0, N-acetals

The present invention relates to a process for preparing triazolyl-0, N-acetals and salts of the following structural formula (I) useful as fungicides.

In the above structural formula

R ¹ represents alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, optionally substituted aryl, or aralkyl, where the aryl moiety may be optionally substituted,

R ² , R ⁴ is one of the groups mentioned for R ¹ and R ² may be hydrogen.

Az is a 1, 2, 4-triazolyl- (1), 1, 2, 4-triazolyl- (4), or 1, 2, 3-triazolyl- (1) group, which may be optionally substituted .

For example, triphenyl-imidazole such as triphenylimidazole and triphenyl 1, 2, 4-triazole, and 1, 2, 4-triazole, etc., have good fungicidal action, US Pat. No. 3,321,366 And Belgian Patent No. 738,095. However, their effects were not satisfactory, especially when used in small or low concentrations. In addition, zinc ethylene-1 and 2-bis-dithiocarbamates, such as Phytophthora infestans, which cause blight in potatoes and tomatoes, and various soil fungi It is already known that it shows a good fungicidal effect against. However, the effect is not always satisfactory when used on dressings.

The compounds according to the invention exhibit strong fungicidal properties.

R ¹ is straight or branched chain alkyl having 1 to 8 carbon atoms (particularly 1 to 4), straight or branched chain alkenyl or alkynyl having 2 to 6 carbon atoms (particularly 3 to 6), and having 6 to 6 carbon atoms Substituted with 10 aryl or substituted with alkyl having 6 to 10 carbons in the aryl moiety and 1 to 2 carbon atoms in the alkyl moiety (with substituents selected from halogen, in particular fluorine, chlorine or cyanogen) 5 to 7 carbon atoms ( In particular 5 to 6) linear or branched cycloalkyl or cyclo alkenyl, 1 to 4 carbon atoms (especially 1 to 2) alkoxy, in particular 1 to 5 halogen atoms such as fluorine or chlorine and 1 to 4 carbon atoms Halogenated alkyls having two, halogenated alkyls having 3 to 5 halogen atoms such as fluorine or chlorine and halogenated alkylthio having 1 to 2 carbon atoms (e.g. chloro difluoromethylthio), 1 to 4 carbon sources in the alkoxy moiety Cut Gajik and a phenyl group and a nitro or O-P- car position is beulkok isochronous.

R ² is hydrogen, straight or branched chain alkyl of 1 to 6 carbon atoms (particularly 1 to 4), straight or branched chain alkenyl of 2 to 6 carbon atoms (particularly 2 to 4 carbon atoms), 2 to 6 carbon atoms Arkyl having a straight or branched chain (particularly 3 to 5), aralkyl having 6 to 10 carbon atoms in the aryl moiety or aralkyl having 1 to 2 carbon atoms in the alkyl moiety or carbon atom substituted by 6 to 10 aryl carbon atoms 5-7 (particularly 5-6) cycloalkyl or cycloalkenyl, substituents selected from halogen elements such as fluorine or chlorine or cancellation, straight or branched chain alkyl of 1 to 4 carbon atoms and 1 to 2 carbons Halogen atom and the like having 2 to 5 halogen atoms such as fluorine or chlorine.

R ⁴ is straight or branched chain alkyl of 1 to 8 carbon atoms (particularly 1 to 4), straight or branched chain alkenyl of 2 to 6 carbon atoms (particularly 3 to 6 carbon atoms), 2 to 6 carbon atoms (particularly 3 to 6) straight or branched alkynyl, 5 to 7 carbon atoms (especially 5 to 6) cycloalkyl or cycloalkenyl, optionally substituted 6 to 10 aryl or aryl moieties of carbon atoms An optionally substituted arylalkyl having 6 to 10 carbon atoms and 1 to 2 carbon atoms in the alkyl moiety, a substituent selected from halogen elements such as fluorine, chlorine or cancellation, a straight chain of 1 to 6 carbon atoms (especially 1 to 4) Or branched alkyl, halogenated alkyl having 1 to 4 carbon atoms (particularly 1 to 2), halogenated alkyl having 1 to 2 carbon atoms and 1 to 5 halogen elements such as fluorine and chlorine, 1 to 2 carbon atoms Atom and 3 to 5 halogen elements such as fluorine or chlorine Halogenoalkylthio (such as chlorodichloromethylthio), carboalkoxy having 1 to 4 carbons in the alkoxy moiety and a phenyl group and a nitro group in the 0- and P-positions.

Az is one of the following groups:

Hal is halogen such as chlorine or cancellation and 'Alkyl' is CH ₃ .

Compounds of formula (I) have two asymmetric carbon atoms and can therefore be either erythto or tritotypes (both of which are mainly racemate forms).

The compound of formula (I) is prepared as follows. The thiazole derivative of formula (II)

In the above structural formula

R ¹ , R ² and R ⁴ are as above.

Prepared by reduction with a complex hydride, optionally in the presence of a polar solvent.

Surprisingly, the active compounds according to the invention have much stronger bactericidal properties than compounds known in the literature such as triphenyl imidazole, triphenyl-1, 2, 4-triazole and zinc ethylene-1, 2-bis-dithiocarbamate. Indicated. The active compounds according to the invention thus represent technological advances.

For example, when 1-phenoxy-1- [1, 2, 4-triazolyl- (1 ')]-3, 3-dimethylbutan-2-one and sodium borohydride are used as starting materials, the reaction process of the manufacturing method Can be represented by the following diagram.

The following is an example of a starting material of formula (II). [W- (1, 2, 4-triazolyl-1 ')]-[W-phenoxy] -acetophenone, [W- (1, 2, 4-triazolyl-1')]-[W-4 '-Chloroyloxy] -acetophenone, [W- (1, 2, 4-triazolyl-1')]-[W-3'-chlorophenoxy] -acetophenone, [W- (1, 2, 4-triazolyl-1 ')]-[W-2', 4'-dichlorophenoxy] -acetophenone, [W- (1, 2, 4-triazolyl-1 ')]-[W-2' , 4'-dichlorophenoxy] -4-chloro-acetophenone, [W- (1, 2, 4-triazolyl-1 ')]-[W-2', 6'-dichlorophenoxy] -acetophenone , [W- (1, 2, 4-triazolyl-1 ')]-[W-4'-methoxyphenoxy] -acetophenone, [W-methyl]-[W- (1, 2, 4- Triazolyl-1 ')]-[W-4'-chlorophenoxy] -acetophenone, [W-phenyl]-[W- (1, 2, 4-triazolyl-1')]-[W-2 ', 4'-dichlorophenoxy] -acetophenone, [W-methyl]-[W-1, 2, 4-triazolyl-1']-[W-2 ', 5'-dichlorophenoxy] -aceto Phenone, [2- (1, 2, 4-triazolyl-1 ')]-[2- (2', 4'-dichlorophenoxy] -acetaldehyde, [1- (1, 2, 4-triazolyl -1 ')]-[1- (2', 4'-dichlorophenoxy] -propan-2-one, [2- (1, 2, 4-triazolyl-1 ')]-[2-phenoxy] -butan-3-one, [2- (1, 2, 4-triazolyl-1')]-[ 2- (4'-Chlorophenoxy] -butan-3-one, [2- (1, 2, 4-triazolyl-1 ')]-[4'-fluorophenoxy)]-butane-3- On, [2- (1, 2, 4-triazolyl-1 ')]-[2- (2', 4'-dichlorophenoxy] -butan-3-one, [1- (1, 2, 4 -Triazolyl-1 ')]-[1- (2', 4'-dichlorophenoxy)]-3-methyl-butan-2-one, [2- (1, 2, 4-triazolyl-1) ]-[2- (4'-chlorophenoxy)]-4-methyl-pentan-3-one, [2- (1, 2, 4-triazolyl-1 ')]-[2- (2'- 4'-dichlorophenoxy)]-4-methyl-pentan-3-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (4'-chlorophenoxy)]- 3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (2', 4'-dichlorophenoxy)]-3, 3- Dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (2', 5'-dichlorophenoxy)]-3, 3-dimethyl-butane- 2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (2', 6'-dichlorophenoxy)]-3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (2', 4 ', 6'-trichloro Phenoxy)]-3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (2'-chlorophenoxy)]-3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (4'-bromophenoxy)]-3, 3-dimethyl-butane- 2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (4'-fluorophenoxy)]-3, 3-dimethyl-butan-2-one, [1 -(1, 2, 4-triazolyl-1 ')]-[1-4'-dimethylphenoxy)]-3, 3-dimethyl-butan-2-one, [1- (1, 2, 4- Triazolyl-1 ')]-[1- (4'-methoxyphenoxy)] 3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1')] -[1- (4'-tert-butylphenoxy)]-3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- ( 4'-isopropylphenoxy)]-3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1 ')]-[1- (2'-methyl-4 '-Chlorophenoxy)]-3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1')]-[1- (4'-trifluoromethylphenoxy C)]-3,3-dimethyl-butan-2-one, [1- (1,2,4-triazolyl-1 ')]-[1- (4'-nitrophenoxy)]-3, 3 -Dimethyl-butan-2-one, [1- (1, 2, 4-triazole) -1 ')]-[1- (2'-nitrophenoxy)]-3, 3-dimethyl-butan-2-one, [1- (1, 2, 4-triazolyl-1)]-1- (4-fluorodichloromethylmercaptophenoxy) -3, 3-dimethyl-butan-2-one, 1- (1, 2, 4-triazolyl-1) -1- (0-diphenoxy)- 3, 3-dimethyl-butan-2-one, 1- (1, 2, 4-triazolyl-1) -1- (0-diphenoxy) -3, 3-dimethyl-butan-2-one, 2 -(1, 2, 4-triazolyl-1) -2-phenoxy-4, 4-dimethyl-pentan-3-one, 2- (1, 2, 4-triazolyl-1) -2- (4 -Fluorophenoxy) -4, 4-dimethyl-pentan-3-one, 2- (1, 2, 4-triazolyl-1) -2- (2, 4-dichlorophenoxy-4, 4-dimethyl -Pentan-3-one, 1-phenyl-1- (1, 2, 4-triazolyl-1) -1- (4-fluorophenoxy) -3, 3-dimethyl-butan-2-one, 1 -Phenyl-1- (1, 2, 4-triazolyl-1) -1- (2, 4-dichlorophenoxy) -3, 3-dimethyl-butan-2-one, 2- (1, 2, 4 -Triazolyl-1) -2- (2,4-dichlorophenoxy) -1-cyclohexyl-ethan-1-one, 2- (1, 2, 4-triazolyl-1) -2- (2, 4-dichlorophenoxy) -1-cyclopentyl-ethan-1-one, 2- (1, 2, 4-triazolyl-1)- 2- (2, 4-dichlorophenoxy) -3-cyclohexyl-propan-3-one.

Triazole derivatives of formula (II) which can be used in the present invention are not yet described in the literature, but were dealt with in part in German Patent Application No. 2201063.5 of January 11, 1972. The derivatives are prepared by, for example, reacting the halogenoether-ketone with 1, 2, 4-triazole in a stoichiometric ratio in the presence of a solvent, diluent or acid binder at a temperature of 80 to 120 ° C. Of particular remarkable mention among other manufacturing processes is the reaction of hydroxyether-ketone with 1, 2, 4-triazole in the presence of a dehydrating agent and a diluent at a temperature of 140 to 200 ° C.

Depending on the manufacturing process or working conditions, the triazole derivatives of formula (II) are obtained as 1, 2, 4-triazolyl- (4) derivatives or as 1, 2, 4-triazolyl- (1) derivatives. It is also obtained as a mixture of the two forms of the compound because of the thixotropic nature of 2,4-triazole.

Salts of the compounds of formula (I) which can be used are salts with physiologically toxic acids. Preferred acids are hydrobromic acids such as hydrobromic acid, in particular hydrochloric acid and phosphoric acid, mono- or bi-functional carboxylic acids, acetic acid, maleic acid, succinic acid, fumaric acid, tartabul, citric acid, salicylic acid, sorbic acid and lactic acid. Carboxylic acids and 1, 5-naphthalene-disulfonic acids.

In the preparation method of the present invention, a suitable diluent of the reaction is a polar organic solvent, for example, alcohols such as methanol, ethanol, butanol and isopropanol, ethers such as diethyl ether or tetrahydrofuran. Usually, the reaction is carried out at 0 ° to 30 °, preferably at 0 ° to 20 °. In the preparation method of the present invention, about 1 mole of a plurality of small compounds such as sodium borohydride or lithium alanate is used per mole of the compound of formula (II). To isolate the compound of formula (I), the residue is treated with hydrochloric acid and the solution is purified with alkamine and extracted with an organic solvent. Further work follows the usual method.

The compound according to the present invention has a strong fungicidal action and does not harm the crops, so it can be used as a plant protection antifungal agent. Fungicides are used to protect plants that sterilize archimisets, picomisites, ascormisheets, basidiomicits and puncture impetentiates. The compounds according to the invention have a very wide range of action and can be used to kill pathogens that can carry parasites and seeds that harm the subterranean or surface parts of plants. The compounds show excellent action in killing parasites, particularly on the surface parts of plants (eg, erythrope, phosphodopair, sparrowoteca, venturia or pyricuria species). It is also effective in rust and black rot bacteria (such as wheat worms).

It is worth noting that the compounds according to the invention are effective not only in prevention but also in treatment. It can be used even after infection. The compound can be used to protect the plant from germs by immersing it in the ground, in the ground, or in the city. The compounds according to the invention can be made in the form of solutions, emulsions, suspensions, ointments, powder granules and the like. In a known method, for example, a surfactant, that is, an emulsifier and / or a dispersant and / or a foaming agent may be used to obtain a mixture of the present compound and an extender (liquid, solid, liquefied gas diluent or medium). When water is used as an extender, an organic solvent can be used as a cosolvent. Liquid diluents or mediators include aromatic hydrocarbons (e.g. xylene, toluene, benzene or alkyl naphthalene), aromatic or aliphatic hydrocarbons (e.g. chlorobenzene, chloroethylene or methylene chloride) treated with chlorine, aliphatic hydrocarbons (e.g. cyclohexane or Paraffin), alcohols (e.g. butanol, glycol or ethers or esters thereof), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), and strong polar solvents (e.g. dimethylformamide, Dimethyl sulfaoxide or acetonitrile and the like). Liquefied gas diluent means a gaseous liquid at room temperature and atmospheric pressure, and examples thereof include aerosol propalant such as halogenated hydrocarbon and aerosol.

Solid diluents or mediators include natural underground minerals (e.g. kaolin, mud, talc, quartz, arapulgite, montmorillonite or diatomaceous earth) or artificial minerals (dispersed acidic acid, alumina or silicate). . Suitable examples of emulsifiers or foaming agents (foaming agents) include, but are not limited to, anionic or anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers (eg alkylarylpolyglycol ethers), alkylsulfonates, alkylsulfanates, Arylsulfonate, albumin hydrolyzate, and the like, and dispersants include lignin sulfite consumption solution and methylcellulose.

The compounds according to the invention can be represented in mixtures with other compounds. Other compounds include fungicides, insecticides, acaricides, nematicides, herbicides, chasing drugs, growth regulators, plant nutrients and land improvers.

Such products have a weight of 1 to 95% (mainly 5 to 90%) of the compound.

The compound is used in the form in which it is made or in an easy-to-use form (eg, solution, emulsion, suspension, powder, ointment, granule, etc.) obtained. When used as a leaf fly fungicide, the concentration of the compound is very wide, usually from 0.1 to 0.00001%, especially from 0.05 to 0.0001% per middle ditch. In the treatment of seeds, the amount of the compound is usually 0.001 to 50 grams per kilogram of seed (especially 0.01 to 10 grams per kilogram). When killing bacteria in the soil, 1 to 1,000 grams (particularly 10 to 200 grams) of the present compound per cubic meter of soil is required. The compounds according to the invention show good bacteriostatic action.

The compounds of the present invention have bactericidal properties in mixtures with diluents or mediators of solids or gases or with mediators with liquid diluents or surfactants. It can be sterilized by administering only the present compound to the fungal or fungal habitat, or by administering a mixture containing the active ingredient or a mixture of diluents or mediators. The crops can be protected from fungi before or during the growth of the compounds alone or in the form of a mixture with diluents or mediators.

The bactericidal action of this compound is obvious from the following test examples.

[Test Example 1]

Eritife Test / Control

Solvent: Acetone (4.7% of all Jungnang)

Emulsifier: Alkylaryl Polyglycol Ether (0.3% of the total weight)

Water: 95% of all Jungnang

In order to achieve a suitable concentration for the spray liquid, as much solvent as mentioned in the present compound is mixed and water containing the adduct described above is mixed and diluted by the above-mentioned amount. The young cucumbers with three leaves were sprinkled with liquid until the drops dripping. The cucumbers were left in the greenhouse for 24 hours to dry. To inoculate the fungus sprinkled conidia of the fungus E. Riccife Sichorea Lum. It was then transferred to a greenhouse at 23-24 ° C. relative humidity 75%. After 12 days, the transmission of cucumber was the same as the control plants inoculated with the bacteria without any treatment. 0% means no infection and 100% means that the infection is as large as the control plants. The working compound, its concentration and the results are as follows.

TABLE 1

Erycife exam

[Test Example 2]

Eritife Test / Infiltration

Solvent: Acetone (4.7% of all Jungnang)

Emulsifier: Alkylaryl Polyglycol Ether (0.3% of the total weight)

Water: 95% of all Jungnang

Mix as much solvent as mentioned in the working compound to bring the appropriate concentration to the water and dilute as much as mentioned the water containing the adduct described. Cucumbers grown on standard soil were poured 20 ml of water with the stated concentration of this compound per 100 ml of soil three times a week at the stage of one or two leaves. Plants treated in this way were then infected with conidia of the fungus E. recipe Sicoraciarum. This was transferred to a greenhouse with a temperature of 23 to 24 ° C. relative atmospheric humidity of 70%. After 12 days, the transmission of cucumber was the same as the control plants inoculated with the bacteria without treatment. 0% means no transmission and 100% means hepatitis is as large as that of experimental control plants. Working compound The concentration of the compound and the result are as follows.

TABLE 2

[Test Example 3]

Grape Spare Test (Apple Powder Mold Disease) / Prevention

Solvent: Acetone (4.7% of all Jungnang)

Emulsifier: Alkylaryl Polyglycol Ether (0.3% of the total weight)

Water: 95% of all Jungnang

Mix the solvent as much as mentioned in the working compound and mix and dilute the water containing the adduct described as much as mentioned to bring the concentration to the spray. At the stage of the leaves 4 to 6, the fruit juice was sprinkled until the water droplets dipped on the fruiting apple tree. It was placed in a greenhouse with a temperature of 20 ° and a relative atmospheric humidity of 70% for 24 hours. At this time, sprinkled spores of apple powdery mildew grape sapphire podcophaera leucotricha salm was inoculated with bacteria and transferred to a greenhouse with a temperature of 21 to 23 ℃ relative atmospheric humidity of about 70%. After 10 days of inoculation, live infections were the same as the control plants inoculated. 0% means no infection and 100% means that the infection is as large as the control plants. The working compound, its concentration and the results are as follows.

TABLE 3

[Test Example 4]

Germination Test / Grain Grain Fungal Disease / Prevention (Leave Breaking Group) Action To prepare a compound, the effective compound (middle 0.25 part) is placed in dimethylformamide (weight 25 parts) and an emulsifier (weight 0.06 parts). (975 parts by weight) was added. Diluted as water to the final concentration appropriate for the spray.

To test for prophylaxis, young barley (one leaf) of Amsel varieties was sprayed with a preparation of the compound until dewy wet. After drying, the barley was sprinkled with spores of Erysiphe graminis var hordei.

Irradiation after 6 days at a temperature of 21 to 22 ° C. and an air humidity of 80 to 90% showed a small mold lump in barley. The degree of infection showed the same rate of infection as the untreated control plants. 0% means no infection and 100% means the same infection rate as untreated. The greater the action of the compound, the less the infection rate of powdery mildew disease. The working compound, the concentration of the compound at the time of spraying and the degree of infection are shown in the table below.

TABLE 4

[Test Example 5]

Powdery mildew disease test (Erishipei Graminis bar, Hordai) of barley / permeability

[Vaginal grain germination]

The compound used is powdered to the seed. Mix a mixture of equal parts of talc and diatomaceous earth with the specific functional compound to obtain a powdered mixture of the desired final concentration of the functional compound. For seed treatment, add barley seeds and shake in a closed glass jar containing the extended compound. Sprinkle the seeds in 2 × 3 grain proportions in a pot of 2 cm in diameter with a compound of 1 part volume of standard stopper soil and 1 part volume of quartz sand. Germination appeared under good conditions of the greenhouse. Seven days after sowing, barley was already the first leaf, at which time was sprinkled with Erichi Graminis bar, Hordai, spores, and further grown by exposure to light at a temperature of 21-22 ° C. and a relative atmospheric humidity of 80-90% for 16 hours. Within 6 days, a typical powdery mildew lump appeared on the leaves. The degree of infection was the infection rate of the untreated control. 0% means no infection and 100% means the same infection rate as untreated control. The greater the action of the compound, the less the infection rate of powdery mildew disease. The active compounds, the concentrations of the compounds coated on the seeds, the amount coated on the seeds and the infection rate of powdery mildew are shown in the table below.

TABLE 5

[Test Example 6]

Fushicladium Test (Apple Disease) / Control

Solvent: Acetone (4.7% of total weight)

Emulsifier: alkylaryl polyglycol ether (0.3% of total weight)

Water: 95% of total weight

To achieve a concentration suitable for sparging, the concentrate was diluted by mixing the compounds in the amounts described above with water containing the adducts described above in the amounts mentioned above. The young apple seeds in 4 to 6 leaf stages were sprayed with spray until the drops dripping. The temperature was kept in a greenhouse of 70% relative air humidity for 24 hours. Then, it was inoculated with a conidia of spores of organic matter (Fuscilardium danthitiscum Hukel), which causes apple disease, and left for 18 hours in a humid room with a temperature of 18 to 20 ° C. and a relative atmospheric humidity of 100%. It was then kept in the greenhouse for 14 days. After 15 days of inoculation, infection of seedlings showed the same rate as the control group inoculated with the group. 0% means no infection and 100% means the same infection as the control plants. The working compounds, the concentrations of the working compounds and the results are shown in the following table.

TABLE 6

The process for the preparation of the compounds according to the invention is apparent by the following examples.

Example 1

31.4 g of ω- [4'-chlorophenoxy] -ω- [1,2,4-triazolyl- (1 ')]-acetophenone was dissolved in 300 ml of methanol and 3 g (0.08 mol) of sodium hydroxide. 0.1 mole of boron is mixed with ice and placed in this solution until cooled. The reaction mixture is stirred for 1 hour at room temperature and the solvent is distilled in vacuo for 1 hour. The residue is diluted with dilute hydrochloric acid and the solution is briefly heated and filtered. The filtered water is purified alkylin with sodium hydroxide solution. The precipitate formed is filtered and placed in ethyl acetate. After distilling the ethyl acetate, the oil remained, which was determined as ligroin to powder. 25 g (98%) of 1- [4'-chlorophenoxy] -1- [1, 2, 4-triazolyl- (1 ')]-2-phenyl-ethanol at a melting point of 117 DEG C after recrystallization from ligroin / isopropanol Is obtained.

[Production of Intermediate]

0.1 mol of 32.5 g (0.1 mol) of ω-bromo-ω- (4'-chlorophenoxy) -acetophenone and 0.44 mol of 30 g of 1, 2, 4-triazole are dissolved in 240 acetonitrile and the solution Heated under reflux for 48 hours. After distilling off the solvent, the residue was taken up in 800 ml of water. The aqueous solution was extracted repeatedly with methylene chloride and the methylene chloride solution was washed twice with 200 ml of water, dried over sodium sulfate and the solvent was distilled off in vacuo. The residue had crystallized out and could be recrystallized from ligroin / isopropanol (2: 1) and the melting point was 98-100 ° C. Ω-Bromo-ω- (4'-chlorophenoxy) -acetophenone required as starting material as an intermediate test aid is 4-chlorophenol and ω-chloroacetophenone, and the resulting ω- (4'-chlorophenoxy Obtained by condensation with) -acetophenone and its melting point was 71 ° C.

Example 2

587 g (2 moles) of 1- (4'-chlorophenoxy) -1- [1, 2, 4-triazolyl- (1 ')]-3 and 2 moles of 3-dimethyl-butan-2-one are methanol Dissolved in 3 l. 80 g (2 mol) of sodium boron hydride was added to it, and it stirred at the temperature of 5 g under the temperature of 0-10 degreeC, stirring. The mixture was stirred at a temperature of 5 to 10 ° C. for 2 hours and at room temperature for 12 hours. The mixture was then cooled to 10 ° and 300 g (3 mol) of concentrated hydrochloric acid were added at 10-20 ° C. After stirring for 6 hours at room temperature, the resulting suspension was diluted with 3.8 liters of water containing 400 g (4.8 mol) of sodium bicarbonate. The precipitate formed here was filtered. 502 g of 85% 1- (4'-chlorophenoxy) -1- [1, 2, 4-triazolyl- (1 ')]-3, 3-dimethyl-butan-2-ol (melting point 112 to 117 C) was obtained.

Example 3

[Eritsu type and Thrio type]

29.5 g (0.114 mol) of 1-phenoxy-1- [1, 2, 4-triazolyl- (1 ')]-3, 3-dimethyl-butan-2-one are dissolved in 250 ml of methanol and 5.8 g (0.15 mol) of sodium boron hydride was cooled while stirring and added at a temperature of 0 to 5 ° C. After stirring for 12 hours at room temperature the mixture was reacted with 20 ml of concentrated hydrochloric acid and 250 ml of saturated sodium bicarbonate solution as described in Example 2. The suspension containing sodium bicarbonate was extracted twice with 150 ml of methylene chloride. The combined organic extracts were washed with 100 ml of water and dried until neutral to remove the solvent in vacuo. The resulting oil was boiled with hot petroleum ether. Hot filtered and dried crystal residues (a) were formed. The filtrate was removed in vacuo and the residue (B) was triturated with petroleum ether and some ether. 23.4 g (79%) containing an erythro type (melting point 132 ° C) of 4.1 g (residue (A)) and a trio type (melting point 88 to 94 ° C) of 19.3 g (residue (B)) ) -Phenoxy-1- [1, 2, 4-triazolyl- (1 ')]-3 and 3-dimethyl-butan-2-one were obtained.

Compounds of the following structural formulas were similarly obtained.

Claims (1)

A process for preparing triazolyl O, N-acetal of formula (I), characterized in that the triazole derivative of formula (II) is reacted with boronhydride sodium in the presence of alcohol as solvent at 0 to 30 ° C.

In the above structural formula R ¹ is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, optionally substituted aryl or aralkyl (aryl moieties may be optionally substituted), R ² and R ⁴ are ^one of the groups mentioned in R ¹ , R ² can be hydrogen A ₂ is an optionally substituted group of 1, 2, 4-triazolyl- (1) or 1, 2, 4-triazolyl- (4) or 1, 2, 3-triazolyl- (1).